Avoiding Errors in Electrochemical Measurements: Effect of Frit Material on the Performance of Reference Electrodes with Porous Frit Junctions

Maral P S Mousavi, Stacey A. Saba, Evan L. Anderson, Marc A. Hillmyer, Philippe Buhlmann

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In many commercially available and in-house-prepared reference electrodes, nanoporous glass frits (often of the brand named Vycor) contain the electrolyte solution that forms a salt bridge between the sample and the reference solution. Recently, we showed that in samples with low ionic strength, the half-cell potentials of reference electrodes comprising nanoporous Vycor frits are affected by the sample and can shift in response to the sample composition by more than 50 mV (which can cause up to 900% error in potentiometric measurements). It was confirmed that the large potential variations result from electrostatic screening of ion transfer through the frit due to the negatively charged surfaces of the glass nanopores. Since the commercial production of porous Vycor glass was recently discontinued, new materials have been used lately as porous frits in commercially available reference electrodes, namely frits made of Teflon, polyethylene, or one of two porous glasses sold under the brand names CoralPor and Electro-porous KT. In this work, we studied the effect of the frit characteristics on the performance of reference electrodes, and show that the unwanted changes in the reference potential are not unique to electrodes with Vycor frits. Increasing the pore size in the glass frits from the <10 nm into the 1 μm range or switching to polymeric frits with pores in the 1 to 10 μm range nearly eliminates the potential variations caused by electrostatic screening of ion transport through the frit pores. Unfortunately, bigger frit pores result in larger flow rates of the reference solution through the pores, which can result in the contamination of test solutions.

Original languageEnglish (US)
Pages (from-to)8706-8713
Number of pages8
JournalAnalytical Chemistry
Issue number17
StatePublished - Sep 6 2016

Bibliographical note

Funding Information:
This project was partially supported by a Graham N. Gleysteen Excellence Fellowship and a University of Minnesota Doctoral Dissertation Fellowship to M.P.S.M., a NSF Graduate Research Fellowship to S.A.S., the National Science Foundation (DMR- 1609459), and Grant RL-0012-12 from the Initiative for Renewable Energy and the Environment of the University of Minnesota.

Publisher Copyright:
© 2016 American Chemical Society.

Copyright 2017 Elsevier B.V., All rights reserved.

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